Epitaxial silicon wafer with intrinsic gettering and a method for the preparation thereof

ABSTRACT

A wafer is characterized in that the wafer has a non-uniform distribution of crystal lattice vacancies, wherein the concentration of crystal lattice vacancies in the bulk layer are greater than the concentration of crystal lattice vacancies in the front surface layer. In addition, the front surface of the wafer has an epitaxial layer, having a thickness of less than about 2.0 μm, deposited thereon. A process comprises heating a surface of a wafer starting material to remove a silicon oxide layer from the surface and depositing an epitaxial layer onto the surface to form an epitaxial wafer. The epitaxial wafer is then heated to a soak temperature of at least about 1175° C. while exposing the epitaxial layer to an oxidizing atmosphere comprising an oxidant, and the wafer is cooled at a rate of at least about 10° C./sec.

CROSS-REFERENCE TO RELATED APPLICATION

This is a division of application Ser. No. 09/859,094, filed May 16,2001, now U.S. Pat. No. 6,537,655, which is a division of applicationSer. No. 09/250,908, filed Feb. 16, 1999, now U.S. Pat. No. 6,284,384,which claims the benefit of U.S. Provisional Application No. 60/111,546,filed Dec. 9, 1998.

BACKGROUND OF THE INVENTION

The present invention generally relates to the preparation ofsemiconductor material substrates, especially silicon wafers, which areused in the manufacture of electronic components. More particularly, thepresent invention relates to a single crystal silicon wafer and a methodfor the preparation thereof. This wafer comprises a surface having anepitaxial silicon layer deposited thereon, and forms an ideal,non-uniform depth distribution of oxygen precipitates during the heattreatment cycles of essentially any electronic device manufacturingprocess.

Single crystal silicon, which is the starting material for mostprocesses used to fabricate semiconductor electronic components, iscommonly prepared by using the Czochralski (“Cz”) process. Using thismethod, polycrystalline silicon (“polysilicon”) is charged to a crucibleand melted, a seed crystal is brought into contact with the moltensilicon, and a single crystal is grown by slow extraction. The firstportion of the crystal to be formed during the extraction process is athin neck. After formation of the neck is complete, the diameter of thecrystal is enlarged by decreasing the pulling rate and/or the melttemperature until the desired or target diameter is reached. Acylindrical main body of the crystal which has an approximately constantdiameter is then grown by controlling the pull rate and the melttemperature while compensating for the decreasing melt level. Near theend of the growth process, but before the crucible is emptied of moltensilicon, the crystal diameter is reduced gradually to form an end-cone.Typically, the end-cone is formed by increasing the crystal pull rateand heat supplied to the crucible. When the diameter becomes smallenough, the crystal is then separated from the melt.

A number of defects in single crystal silicon form in the crystal growthchamber as the crystal cools after solidification. Such defects arise,in part, due to the presence of an excess (i.e., a concentration abovethe solubility limit) of intrinsic point defects, which are known ascrystal lattice vacancies and silicon self-interstitials. Siliconcrystals grown from a melt are typically grown with an excess of one orthe other type of intrinsic point defect. It has been suggested that thetype and initial concentration of these point defects in the silicon aredetermined at the time of solidification and, if these concentrationsreach a level of critical supersaturation in the system and the mobilityof the point defects is sufficiently high, a reaction (or anagglomeration event) will likely occur. The density of agglomeratedintrinsic point defects in Cz silicon is conventionally within the rangeof about 1×10³/cm³ to about 1×10⁷/cm³. While these values are relativelylow, agglomerated intrinsic point defects are of rapidly increasingimportance to device manufacturers and, in fact, are now seen asyield-limiting factors in device fabrication processes and can severelyimpact the yield potential of the material in the production of complexand highly integrated circuits.

One particularly problematic type of defect is the presence of crystaloriginated pits (“COPs”). The source of this type of defect is theagglomeration of silicon lattice vacancies. More specifically, whensilicon lattice vacancies agglomerate within a silicon ingot, they formvoids. Typically, these voids have an octahedral shape and acharacteristic size of at least about 0.01 μm. When the ingot is slicedinto wafers, these voids are exposed and appear as pits on the surfacesof the wafers. These pits are referred to as COPs.

To date, there generally are three main approaches to dealing with theproblem of agglomerated intrinsic point defects. The first approachincludes methods which focus on crystal pulling techniques to reduce thenumber density of agglomerated intrinsic point defects in the ingot.This approach can be further subdivided into those methods havingcrystal pulling conditions which result in the formation of vacancydominated material, and those methods having crystal pulling conditionswhich result in the formation of self-interstitial dominated material.For example, it has been suggested that the number density ofagglomerated defects can be reduced by (i) controlling v/Go (where v isthe growth velocity and Go is the average axial temperature gradient) togrow a crystal in which crystal lattice vacancies are the dominantintrinsic point defect, and (ii) influencing the nucleation rate of theagglomerated defects by altering (generally, by slowing down) thecooling rate of the silicon ingot from about 1100° C. to about 1050° C.during the crystal pulling process. While this approach reduces thenumber density of agglomerated defects, it does not prevent theirformation. As the requirements imposed by device manufacturers becomemore and more stringent, the presence of these defects will continue tobecome more of a problem.

Others have suggested reducing the pull rate during the growth of thebody of the crystal to a value less than about 0.4 mm/minute. Thissuggestion, however, is also not satisfactory because such a slow pullrate leads to reduced throughput for each crystal puller. Moreimportantly, such a pull rate leads to the formation of single crystalsilicon having a high concentration of self-interstitials. This highconcentration, in turn, leads to the formation of agglomeratedself-interstitial defects and all the resulting problems associated withsuch defects.

A second approach to dealing with the problem of agglomerated intrinsicpoint defects includes methods which focus on the dissolution orannihilation of agglomerated intrinsic point defects subsequent to theirformation. Generally, this is achieved by using high temperature heattreatments of the silicon in wafer form. For example, in European PatentApplication No. 503,816 A1, Fusegawa et al. propose growing the siliconingot at a growth rate in excess of 0.8 mm/minute, and heat treating thewafers which are sliced from the ingot at a temperature in the range of1150° C. to 1280° C. to reduce the defect density in a thin region nearthe wafer surface. The specific treatment needed will vary depending onthe concentration and location of agglomerated intrinsic point defectsin the wafer. Different wafers cut from a crystal which does not have auniform axial concentration of such defects may require differentpost-growth processing conditions. Further, such wafer heat treatmentsare relatively costly, have the potential for introducing metallicimpurities into the silicon wafers, and are not universally effectivefor all types of crystal-related defects.

A third approach to dealing with the problem of agglomerated intrinsicpoint defects is the epitaxial deposition of a thin crystalline layer ofsilicon onto the surface of a single crystal silicon wafer. This processprovides a single crystal silicon wafer having a surface which issubstantially free of agglomerated intrinsic point defects. Use of thetraditional epitaxial deposition techniques, however, substantiallyincreases the cost of the wafer.

In addition to containing the above-discussed agglomerated pointdefects, single crystal silicon prepared by the Cz method also typicallycontains various impurities, among which is mainly oxygen. Thiscontamination, for example, occurs while the molten silicon is containedin the quartz crucible. At the temperature of the silicon molten mass,oxygen comes into the crystal lattice until it reaches a concentrationdetermined by the solubility of oxygen in silicon at the temperature ofthe molten mass and by the actual segregation coefficient of oxygen insolidified silicon. Such concentrations are greater than the solubilityof oxygen in solid silicon at the temperatures typical for the processesfor the fabrication of electronic devices. Thus, as the crystal growsfrom the molten mass and cools, the solubility of oxygen in it decreasesrapidly. This ultimately results in wafers containing oxygen insupersaturated concentrations.

Thermal treatment cycles which are typically employed in the fabricationof electronic devices can cause the precipitation of oxygen in siliconwafers which are supersaturated in oxygen. Depending on their locationin the wafer, the precipitates can be harmful or beneficial. Oxygenprecipitates located in the active device region of the wafer (i.e.,typically near the surface) can impair the operation of the device.Oxygen precipitates located in the bulk of the wafer, however, arecapable of trapping undesired metal impurities that may come intocontact with the wafer. The use of oxygen precipitates located in thebulk of the wafer to trap metals is commonly referred to as internal orintrinsic gettering (“IG”).

Historically, electronic device fabrication processes have included aseries of steps which were designed to produce silicon having a regionnear the surface of the wafer which is free of oxygen precipitates(commonly referred to as a “denuded zone” or a “precipitate-free zone”)with the balance of the wafer (i.e., the wafer bulk) containing asufficient number of oxygen precipitates for IG purposes. Denuded zoneshave been formed, for example, in a high-low-high thermal sequence suchas (a) oxygen out-diffusion heat treatment at a high temperature (>1100°C.) in an inert gas for a period of at least about 4 hours, (b) oxygenprecipitate nuclei formation at a low temperature (600 to 750° C.), and(c) growth of oxygen (SiO₂) precipitates at a high temperature (1000 to1150° C.). See, e.g., F. Shimura, Semiconductor Silicon CrystalTechnology, pp. 361-367 (Academic Press, Inc., San Diego Calif., 1989)(and the references cited therein).

More recently, however, advanced electronic device manufacturingprocesses, such as DRAM manufacturing processes, have begun to minimizethe use of high temperature process steps. Although some of theseprocesses retain enough of the high temperature process steps to producea denuded zone and sufficient density of bulk precipitates, thetolerances on the material are too tight to render it a commerciallyviable product. Other current highly advanced electronic devicemanufacturing processes contain no out-diffusion steps at all. Becauseof the problems associated with oxygen precipitates in the active deviceregion, therefore, these electronic device fabricators must use siliconwafers which are incapable of forming oxygen precipitates anywhere inthe wafer under their process conditions. As a result, IG potential islost.

In Japanese Patent Application No. 8-24796, Asayama et al. disclose aprocess for imparting intrinsic gettering into a wafer before it is usedin an electronic device manufacturing process. Specifically, Asayama etal. disclose: (a) baking silicon wafers at 1150° C. in a H₂ atmosphere;(b) depositing epitaxial layers onto the surfaces of the wafers attemperatures of 1100, 1150, and 1200° C.; and (c) cooling the wafers atrates of 5, 10, and 15° C./sec. The wafers analyzed by Asayama et al.had a resistivity of no greater than 0.5 Ω-cm and an oxygen density of11×10¹⁷ atoms/cm³ (in other words, about 22 ppm (i.e., 22 oxygen atomsper 1,000,000 total atoms in the wafer)). Asayama et al. conclude thatif the process is used with a temperature of from 1150 to 1250° C. and acooling rate of 10 to 100° C./sec, such wafers will form a desirableoxygen precipitate profile upon being heated over a period of time at atemperature of from 700 to 1000° C.

SUMMARY OF THE INVENTION

Among the objects of the present invention is the provision of a singlecrystal silicon wafer which (a) has an epitaxial surface that isessentially free of crystal originated pits; and (b) forms an ideal,non-uniform depth distribution of oxygen precipitates during a heattreatment cycle of essentially any electronic device manufacturingprocess.

Briefly, therefore, this invention is directed to a single crystalsilicon wafer comprising: (a) two major generally parallel surfaces(i.e., the front and back surfaces); (b) a central plane between andparallel to the front and back surfaces; (c) a front surface layer whichcomprises the region of the wafer extending a distance, D₁, of at leastabout 10 μm from the front surface toward the central plane; and (d) abulk layer which comprises the region of the wafer extending from thecentral plane to the front surface layer. This wafer is characterized inthat the wafer has a non-uniform distribution of crystal latticevacancies wherein (a) the concentration of crystal lattice vacancies inthe bulk layer is greater than the concentration of crystal latticevacancies in the front surface layer, (b) the crystal lattice vacancieshave a concentration profile having a peak density of crystal latticevacancies at or near the central plane, and (c) the concentration ofcrystal lattice vacancies generally decreases from the position of peakdensity toward the front surface of the wafer. In addition, the frontsurface of the wafer has an epitaxial layer deposited thereon. Thisepitaxial layer has a thickness of from about 0.1 to about 2.0 μm.

In another embodiment directed to a single crystal silicon wafer, thewafer comprises: (a) two major generally parallel surfaces (i.e., afront surface and a back surface); (b) a central plane between andparallel to the front and back surfaces; (c) a front surface layer whichcomprises the region of the wafer extending a distance, D₂, of at leastabout 10 μm from the front surface toward the central plane; and (d) abulk layer which comprises the region of the wafer extending from thecentral plane to the front surface layer. In this embodiment, the waferhas a non-uniform distribution of crystal lattice vacancies wherein (a)the concentration of crystal lattice vacancies in the bulk layer isgreater than the concentration of crystal lattice vacancies in the frontsurface layer, (b) the crystal lattice vacancies have a concentrationprofile having a peak density of crystal lattice vacancies at or nearthe central plane, and (c) the concentration of crystal latticevacancies generally decreases from the position of peak density towardthe front surface of the wafer. In addition, the front surface of thewafer has an epitaxial layer deposited thereon. This epitaxial layercomprises a surface having an average light scattering eventconcentration of no greater than about 0.06/cm², as measured by alaser-based auto inspection tool configured to detect light scatteringevents corresponding to polystyrene spheres having diameters of no lessthan about 0.12 μm. Also in this embodiment, the bulk layer comprisesvoids which are at least about 0.01 μm in their largest dimension.

In an additional embodiment directed to a single crystal silicon wafer,the wafer comprises: (a) two major generally parallel surfaces (i.e.,the front and back surfaces), (b) a central plane between and parallelto the front and back surfaces, (c) a front surface layer comprising theregion of the wafer extending a distance of no more than about 100 μmfrom the front surface toward the central plane, and (d) a bulk layercomprising the region of the wafer extending from the central plane tothe front surface layer. In this embodiment, the bulk layer has asubstantially uniform oxygen concentration and a concentration ofcrystal lattice vacancies such that upon subjecting the wafer to anoxygen precipitation heat treatment consisting essentially of annealingthe wafer at 800° C. for about 4 hours and then at 1000° C. for 16hours, the wafer will contain oxygen precipitates having a concentrationprofile in which the peak density of the precipitates in the bulk layeris at or near the central plane with the concentration of theprecipitates in the bulk layer generally decreasing in the direction ofthe front surface layer. In addition, the front surface of the wafer hasan epitaxial layer deposited thereon. This epitaxial layer has athickness of from about 0.1 to about 2.0 μm.

In a further embodiment directed to a single crystal silicon wafer, thewafer comprises: (a) two major generally parallel surfaces (i.e., afront surface and a back surface), (b) a central plane between andparallel to the front and back surfaces, (c) a front surface layercomprising the region of the wafer extending a distance of no more thanabout 100 μm from the front surface toward the central plane, and (d) abulk layer comprising the region of the wafer extending from the centralplane to the front surface layer. In this embodiment, the bulk layer hasa substantially uniform oxygen concentration and a concentration ofcrystal lattice vacancies such that upon subjecting the wafer to anoxygen precipitation heat treatment consisting essentially of annealingthe wafer at 800° C. for about 4 hours and then at 1000° C. for 16hours, the wafer will contain oxygen precipitates having a concentrationprofile in which the peak density of the precipitates in the bulk layeris at or near the central plane with the concentration of theprecipitates in the bulk layer generally decreasing toward the frontsurface layer. The bulk layer also comprises voids which are at leastabout 0.01 μm in their largest dimension. The front surface of the waferhas an epitaxial layer deposited thereon. This epitaxial layer comprisesa surface having an average light scattering event concentration of nogreater than about 0.06/cm², as measured by a laser-based autoinspection tool configured to detect light scattering eventscorresponding to polystyrene spheres having diameters of no less thanabout 0.12 μm.

This invention is also directed to a process for the preparation of asilicon wafer comprising a surface having an epitaxial layer depositedthereon. In one embodiment, the process comprises first heating asurface of a wafer starting material in an oxidant-free atmosphere toremove a silicon oxide layer from the surface. Within about 30 secondsafter removing the silicon oxide layer from the surface, the surface isexposed to an atmosphere comprising silicon to deposit a siliconepitaxial layer onto the surface to form an epitaxial wafer. Theepitaxial wafer is then heated to a soak temperature of at least about1175° C. while exposing the epitaxial layer to an oxidizing atmospherecomprising an oxidant. Afterwards, the heated epitaxial wafer is cooledat a rate of at least about 10° C./sec.

In another embodiment directed to a process for the preparation of asilicon wafer comprising a surface having an epitaxial layer depositedthereon, the process comprises first heating a surface of a waferstarting material to a temperature of at least about 1100° C. in anoxidant-free atmosphere to remove a silicon oxide layer from thesurface. Within about 30 seconds after the surface reaches 1100° C., thesurface is exposed to an atmosphere comprising silicon to deposit asilicon epitaxial layer onto the surface to form an epitaxial wafer. Theepitaxial wafer is then heated to a soak temperature of at least about1175° C. while exposing the epitaxial layer to an oxidizing atmospherecomprising an oxidant. Afterwards, the heated epitaxial wafer is cooledat a rate of at least about 10° C./sec.

In another embodiment directed to a process for the preparation of asilicon wafer comprising a surface having an epitaxial layer depositedthereon, the process comprises first heating a surface of a waferstarting material to a temperature of at least about 1150° C. in anoxidant-free atmosphere to remove a silicon oxide layer from thesurface. Within about 30 seconds after the surface reaches 1150° C., thesurface is exposed to an atmosphere comprising silicon to deposit asilicon epitaxial layer onto the surface to form an epitaxial wafer. Theepitaxial wafer is then heated to a soak temperature of at least about1175° C. while exposing the epitaxial layer to an oxidizing atmospherecomprising an oxidant. Afterwards, the heated epitaxial wafer is cooledat a rate of at least about 10° C./sec.

In an additional embodiment directed to a process for the preparation ofa silicon wafer comprising a surface having an epitaxial layer depositedthereon, the process comprises first depositing an epitaxial layer ontoa surface of a wafer to form an epitaxial wafer. The epitaxial wafer isthen heated to a soak temperature of at least about 1175° C. whileexposing the epitaxial layer to an oxidizing atmosphere comprising anoxidant. Afterwards, the heated epitaxial wafer is cooled at a rate ofat least about 10° C./sec. In this embodiment, the epitaxial layer isnot contacted with a post-epitaxial-deposition cleaning solution beforethe epitaxial wafer is heated to the soak temperature.

In a further embodiment directed to a process for the preparation of asilicon wafer comprising a surface having an epitaxial layer depositedthereon, the process comprises first heating a wafer comprising asurface with an epitaxial layer deposited thereon to a soak temperatureof at least about 1175° C. while exposing the epitaxial layer to anoxidizing atmosphere comprising an oxidant. The heated wafer is thencooled at a rate of at least about 10° C./sec. In this embodiment, theepitaxial layer has a thickness of at least about 0.1 μm and less than2.0 μm.

In another embodiment directed to a process for the preparation of asilicon wafer comprising a surface having an epitaxial layer depositedthereon, the process comprises first depositing an epitaxial layer ontoa surface of a wafer starting material to form an epitaxial wafer. Theepitaxial wafer is heated to a soak temperature of at least about 1175°C. while exposing the epitaxial layer to an oxidizing atmospherecomprising an oxidant. Afterwards, the heated epitaxial wafer is cooledat a rate of at least about 10° C./sec. In this embodiment, the surfaceof the wafer starting material (before the epitaxial layer is depositedonto the surface) has an average light scattering event concentration ofat least about 0.5/cm² as measured by a laser-based auto inspection toolconfigured to detect light scattering events corresponding topolystyrene spheres having diameters of no less than about 0.12 μm.

In yet another embodiment directed to a process for the preparation of asilicon wafer comprising a surface having an epitaxial layer depositedthereon, the process comprises first heating a surface of a waferstarting material to a temperature of at least about 1150° C. in anatmosphere consisting essentially of H₂ to remove a silicon oxide layerfrom the surface. Within about 10 seconds after the surface reaches1150° C., the surface is exposed to an atmosphere comprising SiHCl₃ todeposit a silicon epitaxial layer onto the surface to form an epitaxialwafer. The epitaxial wafer is then heated to a soak temperature of atleast about 1175° C. while exposing the epitaxial layer to an oxidizingatmosphere comprising O₂. Afterwards, the epitaxial wafer is cooled at arate of at least about 20° C./sec from the soak temperature to about250° C. below the soak temperature. In this embodiment, the epitaxiallayer has a thickness of from about 0.65 to 1.0 μm, and theconcentration of the O₂ in the oxidizing atmosphere is from about 300 toabout 500 ppm.

This invention is also directed to a process for heating and rapidlycooling a single crystal silicon wafer in a reactor constructed fordepositing a silicon epitaxial layer onto a surface of a wafer. Thisprocess comprises heating the wafer to a soak temperature of at leastabout 1175° C., and cooling the heated wafer at a rate of at least about10° C./sec. In this embodiment, the wafer is supported on a susceptorduring the heating step and is removed from contact with the susceptorduring the cooling step.

Other features of this invention will be in part apparent and in partpointed out hereinafter.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the preferred structure of a single crystal silicon waferthat may be used as the starting material in accordance with the instantinvention.

FIG. 2 shows an oxygen precipitate profile of a wafer which may beprepared in accordance with a preferred embodiment of the instantinvention.

FIG. 3 is a schematic diagram of the mechanism used in an EPI CENTURA®reactor (Applied Materials, Santa Clara, Calif.) for positioning a waferwithin the reactor. In this figure, the susceptor support shaft 105 andwafer lift shaft 107 are in the exchange position.

FIG. 4 is a schematic diagram of the mechanism used in an EPI CENTURA®reactor for positioning a wafer within the reactor, wherein thesusceptor support shaft 105 and wafer lift shaft 107 are in the homeposition.

FIG. 5 is a schematic diagram of the mechanism used in an EPI CENTURA®reactor for positioning a wafer within the reactor. In this figure, thesusceptor support shaft 105 and wafer lift shaft 107 are in the processposition.

FIG. 6 is a schematic diagram of the mechanism used in an EPI CENTURA®reactor for positioning a wafer within the reactor. This figure showsthe preferred position of the susceptor support shaft 105 and wafer liftshaft 107 when the wafer is being rapidly cooled in accordance with thisinvention to influence the crystal lattice vacancy profile in the wafer.

FIG. 7 is a cross-sectional view of the mechanism used in an EPICENTURA® reactor for positioning a wafer within the reactor. This viewis taken from line 7-7 in FIG. 3.

FIG. 8 shows an oxygen precipitate profile of a wafer which may beprepared in accordance with a preferred embodiment of the instantinvention where the starting material is a void-rich single crystalsilicon wafer.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

In accordance with the present invention, a novel and useful singlecrystal silicon wafer comprising a surface having an epitaxial siliconlayer deposited thereon has been developed. The epitaxial surface of thewafer typically has an average light scattering event concentration ofno greater than about 0.06/cm², as measured by a laser-based autoinspection tool configured to detect light scattering eventscorresponding to polystyrene spheres having diameters of no less thanabout 0.12 μm. In addition, the wafer contains a “template” thatdetermines (or “prints”) the manner in which oxygen will precipitatewhen the wafer is heated during the electronic device manufacturingprocess. Thus, during a heating step of essentially any electronicdevice manufacturing process, the wafer will form (a) a denuded zone ofsufficient depth, and (b) a wafer bulk containing a sufficient densityof oxygen precipitates for IG purposes. Also in accordance with thisinvention, a novel method has been developed for preparing such a singlecrystal silicon wafer. This method may be completed in a matter ofminutes using tools which are in common use in the silicon semiconductormanufacturing industry.

A. Starting Material

The starting material for the ideal precipitating wafer of the presentinvention preferably is a single crystal silicon wafer which has beensliced from a single crystal ingot grown in accordance with any of theconventional variations of the Cz crystal growing method. This method,as well as standard silicon slicing, lapping, etching, and polishingtechniques, are well known in the art and disclosed, for example, in F.Shimura, Semiconductor Silicon Crystal Technology (Academic Press,1989); and Silicon Chemical Etching, (J. Grabmaier, ed.,Springer-Verlag, New York, 1982).

Referring to FIG. 1, the wafer 1 preferably has a front surface 3, aback surface 5, an imaginary central plane 7 between the front and backsurfaces, and a circumferential edge 2 joining the front surface 3 andthe back surface 5. The terms “front” and “back” in this context areused to distinguish the two major, generally planar surfaces of thewafer 1. It should be noted that the front surface 3 is not necessarilythe surface on which an electronic device will subsequently befabricated, nor is the back surface 5 necessarily the major surface ofthe wafer 1 which is opposite the surface on which the electronic deviceis fabricated. In addition, because silicon wafers typically have sometotal thickness variation (TTV), warp, and bow, the midpoint betweenevery point on the front surface and every point on the back surface maynot precisely fall within a plane. As a practical matter, however, theTTV, warp, and bow are typically so slight that to a close approximationthe midpoints can be said to fall within an imaginary central planewhich is approximately equidistant between the front and back surfaces.

The wafer may contain one or more dopants to give the wafer variousdesired properties. For example, the wafer may be a P-type wafer (i.e.,a wafer that has been doped with an element from Group 3 of the PeriodicTable, most typically boron) or an N-type wafer (i.e., a wafer that hasbeen doped with an element from Group 5 of the Periodic Table, mosttypically arsenic). Preferably, the wafer is a P-type wafer having aresistivity of from about 0.004 to about 50 Ω-cm. In a particularlypreferred embodiment, the wafer is a P-type wafer having a resistivityof from about 1 to about 20 Ω-cm. In another particularly preferredembodiment, the wafer is a P-type wafer having a resistivity of fromabout 0.01 to 1.0 Ω-cm.

A wafer prepared using the Cz method typically has an oxygenconcentration anywhere from about 5×10¹⁷ to about 9×10¹⁷ atoms/cm³ (inother words, from about 10 to about 18 ppm (i.e., from about 10 to about18 oxygen atoms per 1,000,000 total atoms in the wafer)) (ASTM standardF-121-80), and most typically from about 6×10¹⁷ to about 8.5×10¹⁷atoms/cm³ (i.e., from about 12 to about 17 ppm). The oxygenprecipitation behavior of the wafer becomes essentially decoupled fromthe oxygen concentration in the ideal precipitating wafer; thus, thewafer starting material may have an oxygen concentration fallinganywhere within or even outside the range attainable by the Cz method.In addition, depending on the cooling rate of the single crystal siliconingot from the melting point of silicon (i.e., about 1410° C.) throughthe range of about 750° C. to about 350° C., oxygen precipitatenucleation centers may form. The presence or absence of these nucleationcenters in the starting material typically is not critical to thepresent invention provided that these centers are capable of beingdissolved by heat-treating the silicon at temperatures not in excess ofabout 1250° C.

This invention is particularly useful when used with void-rich waferstarting materials. The phrase “void-rich wafers” refers to wafers thatcontain a relatively large number of crystal lattice vacancyagglomerations. These agglomerations typically have octahedralstructures which are at least about 0.01 μm in their largest dimension.In the bulk of the wafer, these agglomerations are in the form of voids;whereas at the surface of the wafer, they appear in the form of pits(i.e., COPs). Pits on the surface of a wafer may be detected by alaser-based auto inspection tool (sometimes referred to as a“laser-based surface inspection tool” or a “wafer surface particlecounter”), which detects light scattering events emitted by the pitswhen the surface is scanned by the tool's laser. Examples of suitablecommercially available auto inspection tools include the Surfscan 6220from KLA Tencor (Mountain View, Calif.); and the CR80, CR81, and CR82from ADE Optical Systems Corp. (Charlotte, N.C.). Void-rich waferstarting materials which are particularly preferable for use with thisinvention have an average light scattering event concentration of atleast about 0.5/cm², as measured by a laser-based auto inspection toolconfigured to detect light scattering events corresponding topolystyrene spheres having diameters of no less than about 0.12 μm. Morepreferably, this average light scattering event concentration is fromabout 0.5 to about 10/cm², still more preferably from about 0.5 to about3.5/cm², and most preferably from about 0.6 to about 1.6/cm². Void-richwafers are particularly preferred starting materials because they may besliced from silicon ingots formed by relatively low-cost processes,e.g., the traditional open-architecture Cz processes.

B. Epitaxial Deposition

The single crystal silicon wafer prepared in accordance with thisinvention comprises a surface having an epitaxial silicon layerdeposited thereon. The epitaxial layer may be deposited onto the entirewafer, or, alternatively, onto only a portion of the wafer. Referring toFIG. 1, the epitaxial layer preferably is deposited onto the frontsurface 3 of the wafer. In a particularly preferred embodiment, it isdeposited onto the entire front surface 3 of the wafer. Whether it ispreferred to have an epitaxial layer deposited onto any other portion ofthe wafer will depend on the intended use of the wafer. For mostapplications, the existence or non-existence of an epitaxial layer onany other portion of the wafer is not critical.

As noted earlier, single crystal silicon wafers sliced from ingotsprepared by the Cz method often have COPs on their surfaces. A waferused for integrated circuit fabrication, however, generally is requiredto have a surface which consists essentially of no COPs. A wafer havingan essentially COP-free surface may be prepared by depositing anepitaxial silicon layer onto the surface of the wafer. Such an epitaxiallayer fills in the COPs and ultimately produces a smooth wafer surface.This has been the topic of recent scientific investigations. SeeSchmolke et al., The Electrochem. Soc. Proc., vol. PV98-1, p. 855(1998); Hirofumi et al., Jpn. J. Appl. Phys., vol. 36, p. 2565 (1997).Applicants have discovered in accordance with this invention that COPson a wafer surface may be eliminated by using an epitaxial silicon layerthickness of at least about 0.1 μm. Preferably, the epitaxial layer hasa thickness of at least about 0.1 μm and less than about 2 μm. Morepreferably, the epitaxial layer has a thickness of from about 0.25 toabout 1 μm, and most preferably from about 0.65 to about 1 μm.

It should be noted that the preferred thickness of the epitaxial layermay vary if the epitaxial layer is used to impart electrical propertiesto the wafer surface in addition to eliminating COPs. For example,precise control of a dopant concentration profile near the wafer surfacemay be achieved using an epitaxial layer. Where an epitaxial layer isused for a purpose in addition to eliminating COPs, such a purpose mayrequire an epitaxial layer thickness which is greater than the preferredthickness used to eliminate the COPs. In such an instance, the minimumthickness to achieve the additional desired effect preferably is used.Depositing a thicker layer onto the wafer is generally less commerciallydesirable because forming the thicker layer requires a greaterdeposition time and more frequent cleaning of the reaction vessel.

If a wafer has a silicon oxide layer (e.g., a native silicon oxidelayer, which forms on a silicon surface when it is exposed to air atroom temperature and generally has a thickness of from about 10 to about15 Å) on its surface, the silicon oxide layer preferably is removed fromthe surface of the wafer before the epitaxial layer is deposited ontothe surface. As used herein, the phrase “silicon oxide layer” refers toa layer of silicon atoms which are chemically bound to oxygen atoms.Typically, such a silicon oxide layer contains about 2.0 oxygen atomsper silicon atom.

In a preferred embodiment of this invention, removal of the siliconoxide layer is preferably accomplished by heating the surface of thewafer in an atmosphere consisting essentially of no oxidants (mostpreferably, the atmosphere is oxidant-free) until the silicon oxidelayer is removed from the surface. In a particularly preferredembodiment, the surface of the wafer is heated to a temperature of atleast about 1100° C., and more preferably to a temperature of at leastabout 1150° C. This heating preferably is conducted while exposing thesurface of the wafer to an atmosphere comprising a noble gas (e.g., He,Ne, or Ar), H₂, HF gas, or a combination thereof. More preferably, theatmosphere comprises HF gas, H₂, or a combination thereof; atmospherescomprising a noble gas tend to cause pits to form in the surface of thewafer. Most preferably, the atmosphere consists essentially of H₂. Itshould be noted that although atmospheres containing N₂ may be used,such atmospheres are less preferred because they tend to form nitrideson the surface which interfere with subsequent epitaxial deposition onthe surface.

Traditionally, the epitaxial deposition protocols that remove a siliconoxide layer by heating a wafer in the presence of H₂ require the waferto be heated to a high temperature (e.g., from about 1000 to about 1250°C.) and then baked at that temperature for a period of time (i.e.,typically from about 10 to about 90 seconds). It has been discovered inaccordance with this invention, however, that if the surface of thewafer is heated to about 1100° C. (and more preferably, about 1150° C.)in an atmosphere comprising H₂, the silicon oxide layer is removedwithout the subsequent bake step, thereby rendering the bake stepunnecessary. Elimination of the bake step shortens the time required toprepare the wafer and therefore is commercially desirable.

In a preferred embodiment of this invention, the wafer surface is heatedto remove the silicon oxide layer, and then the surface is exposed to anatmosphere containing silicon to deposit the epitaxial layer onto thesurface. More preferably, the surface is exposed with the atmospherecontaining silicon less than 30 seconds after the silicon oxide isremoved, more preferably within about 20 seconds after the silicon oxidelayer is removed, and most preferably within about 10 seconds after thesilicon oxide layer is removed. In a particularly preferred embodiment,the wafer surface is heated to a temperature of at least about 1100° C.(more preferably, at least about 1150° C.), and then is exposed to anatmosphere containing silicon less than 30 seconds after the wafersurface reaches that temperature. More preferably, the surface isexposed to the atmosphere containing silicon within 20 seconds after thewafer surface reaches that temperature, and most preferably less within10 seconds after the wafer surface reaches that temperature. Waiting toinitiate silicon deposition for about 10 seconds after removal of thesilicon oxide layer allows the temperature of the wafer to stabilize andbecome uniform.

During the removal of the silicon oxide layer, the wafer preferably isheated at a rate which does not cause slip. More specifically, if thewafer is heated too quickly, a thermal gradient will develop which willcreate an internal stress sufficient to cause different planes withinthe wafer to shift relative to each other (i.e., slip). Lightly dopedwafers (e.g., a wafer doped with boron and having a resistivity of about1 to about 10 Ω-cm) have been found to be particularly susceptible toslip. To avoid this problem, the wafer preferably is heated from roomtemperature to the silicon oxide removal temperature at an average rateof about 20 to about 35° C./sec.

The epitaxial deposition preferably is carried out by chemical vapordeposition. Generally speaking, chemical vapor deposition involvesexposing the surface of the wafer to an atmosphere comprising silicon inan epitaxial deposition reactor, e.g., an EPI CENTURA® reactor (AppliedMaterials, Santa Clara, Calif.). In a preferred embodiment of thisinvention, the surface of the wafer is exposed to an atmospherecomprising a volatile gas comprising silicon (e.g., SiCl₄, SiHCl₃,SiH₂Cl₂₁ SiH₃Cl, or SiH₄). The atmosphere also preferably contains acarrier gas (most preferably H₂). In one embodiment, the source ofsilicon during the epitaxial deposition is SiH₂Cl₂ or SiH₄. If SiH₂Cl₂is used, the reactor pressure during deposition preferably is from about500 to about 760 Torr. If, on the other hand, SiH₄ is used, the reactorpressure preferably is about 100 Torr. Most preferably, the source ofsilicon during the deposition is SiHCl₃. This tends to be much cheaperthan other sources. In addition, an epitaxial deposition using SiHCl₃may be conducted at atmospheric pressure. This is advantageous becauseno vacuum pump is required and the reactor chamber does not have to beas robust to prevent collapse. Moreover, fewer safety hazards arepresented and the chance of air leaking into the reactor chamber islessened.

During the epitaxial deposition, the temperature of the wafer surfacepreferably is maintained at a temperature sufficient to prevent theatmosphere comprising silicon from depositing polycrystalline silicononto the surface. Generally, the temperature of the surface during thisperiod preferably is at least about 900° C. More preferably, thetemperature of the surface is maintained at from about 1050 to about1150° C. Most preferably, the temperature of the surface is maintainedat the silicon oxide removal temperature.

The rate of growth of the epitaxial deposition preferably is from about3.5 to about 4.0 μm/min when the deposition is conducted underatmospheric pressure. This may be achieved, for example, by using anatmosphere consisting essentially of about 2.5 mole % SiHCl₃ and about97.5 mole % H₂ at a temperature of about 1150° C.

If the intended use of the wafer requires that the epitaxial layerinclude a dopant, the atmosphere comprising silicon also preferablycontains the dopant. For example, it is often preferable for theepitaxial layer to contain boron. Such a layer may be prepared by, forexample, including B₂H₆ in the atmosphere during the deposition. Themole fraction of B₂H₆ in the atmosphere needed to obtain the desiredproperties (e.g., resistivity) will depend on several factors, such asthe amount of boron out-diffusion from the particular substrate duringthe epitaxial deposition, the quantity of P-type dopants and N-typedopants that are present in the reactor and substrate as contaminants,and the reactor pressure and temperature. Applicants have successfullyused an atmosphere containing about 0.03 ppm of B₂H₆ (i.e., about 0.03mole of B₂H₆ per 1,000,000 moles of total gas) at a temperature of about1125° C. and a pressure of about 1 atm. to obtain an epitaxial layerhaving a resistivity of about 10 Ω-cm.

Once an epitaxial layer having the desired thickness has been formed,the atmosphere comprising silicon preferably is purged from the reactionchamber with a noble gas, H₂, or a combination thereof; and morepreferably with H₂ alone. Afterward, the wafer preferably is cooled to atemperature of no greater than about 700° C. and then removed from theepitaxial deposition reactor.

Conventional epitaxial deposition protocols typically include a cleaningstep following epitaxial deposition to remove byproducts formed duringthe epitaxial deposition. This step is used to prevent time-dependenthaze, which results if such byproducts react with air. In addition, thisstep typically forms a silicon oxide layer on the epitaxial surfacewhich tends to passivate (i.e., protect) the surface. Conventionalpost-epitaxial-deposition cleaning methods entail, for example,immersing the epitaxial surface in any of a number of cleaning solutionswhich are well-known to those of ordinary skill in the art. Thesesolutions include, for example, piranha mixtures (i.e., mixtures ofsulfuric acid and hydrogen peroxide), SC-1 mixtures (i.e., mixtures ofH₂O, H₂O₂, and NH₄OH, also known as “RCA standard clean 1”), and SC-2mixtures (i.e., mixtures of H₂O, H₂O₂, and HCl, also known as “RCAstandard clean 2”). See, e.g., W. Kern, “The Evolution of Silicon WaferCleaning Technology,” J. Electrochem. Soc., Vol. 137, No. 6, 1887-92(1990). Many such post-epitaxial-deposition cleaning steps requireexpensive wet cleaning equipment, large volumes of ultra-pure chemicals,additional wafer handling which often leads to additional yield lossesIt has been discovered in accordance with this invention, however, thatthe post-epitaxial-deposition cleaning step is generally not necessarybefore conducting the next step (i.e., the heat treatment step discussedbelow in Section C). This is presently believed to be due to the factthat the heat treatment step is conducted in an atmosphere comprising anoxidant, preferably oxygen gas. The oxidant is believed to react withthe epitaxial deposition byproducts left on the wafer surface after thedeposition. This reaction between the oxidant and the byproductsproduces volatile substances which desorb from the wafer surface. Inaddition to removing the epitaxial deposition byproducts, the oxidantalso forms an oxide layer on the epitaxial layer which passivates theepitaxial layer. Thus, there is no need to use a conventionalpost-epitaxial-deposition cleaning treatment (particularly a treatmentcomprising contacting the wafer with a post-epitaxial-depositioncleaning solution) before conducting the next step of this invention.

C. Heat Treatment to Influence the Precipitation Behavior of Oxygen inthe Wafer in a Subsequent Thermal Processing Step

After epitaxial deposition, the wafer is treated to form a template ofcrystal lattice vacancies within the wafer which causes an ideal,non-uniform depth distribution of oxygen precipitates to form within thewafer when the wafer is heat-treated, such as during a heat treatmentcycle of essentially any electronic device manufacturing process. FIG. 2shows one such oxygen precipitate distribution which may be formed byheat-treating a wafer prepared in accordance with this invention. Inthis particular embodiment, the wafer 1 is characterized by regions 15and 15′ (“denuded zones”) which are free of oxygen precipitates. Thesezones extend from the front surface 3 and back surface 5 to a depth of tand t′, respectively. Preferably, t and t′ are each from about 10 toabout 100 μm, and more preferably from about 50 to about 100 μm. Betweenthe oxygen precipitate-free regions 15 and 15′, there is a region 17which contains a substantially uniform concentration of oxygenprecipitates. For most applications, the oxygen precipitateconcentration in region 17 is at least about 5×10⁸ precipitates/cm³, andmore preferably is about 1×10⁹ precipitates/cm³. It should be recognizedthat the purpose of FIG. 2 is to help acquaint those skilled in the artwith this invention by illustrating merely one embodiment of thisinvention. This invention is not limited to that embodiment. Forexample, this invention may also be used to form a wafer having only onedenuded zone 15 (instead of two denuded zones 15 and 15′).

To form the template of crystal lattice vacancies, the wafer generallyis first heated in an oxidizing atmosphere comprising an oxidant, andthen cooled at a rate of at least about 10° C./sec. The purpose ofheating the wafer is to: (a) form self-interstitial and vacancy pairs(i.e., Frenkel defects) in the crystal lattice which are distributeduniformly throughout the wafer, and (b) dissolve unstabilized oxygenprecipitate nucleation centers present in the wafer. Generally, heatingto greater temperatures results in a greater number of Frenkel defectsbeing formed. The purpose of the cooling step is to produce anon-uniform distribution of crystal lattice vacancies, wherein thevacancy concentration is maximum at or near the center of the wafer, anddecreases in the direction of the surfaces of the wafer. Thisnon-uniform distribution of crystal lattice vacancies is believed to becaused by the fact that a portion of vacancies near the surfaces of thewafer diffuse to the surfaces during the cool down and thereby becomeannihilated, resulting in lower concentrations of vacancies near thesurfaces.

For most applications, the wafer preferably is heated in the oxidizingatmosphere to a soak temperature of at least about 1175° C. Morepreferably, it is heated to a soak temperature of from about 1200 toabout 1300° C., and most preferably from about 1225 to about 1250° C.When the temperature of the wafer reaches the preferred soaktemperature, the wafer temperature preferably is held at the soaktemperature for a period of time. The preferred amount of time generallyis from about 10 to about 15 seconds. In a typical presentlycommercially available epitaxial deposition reactor, the waferpreferably is held at the soak temperature for about 12 to about 15seconds. In a typical presently commercially available RTA furnace, onthe other hand, the wafer preferably is held at the soak temperature forabout 10 seconds.

In one embodiment of this invention, the oxidizing atmosphere comprisesH₂O and H₂. More preferably, however, the oxidant in the oxidizingatmosphere is oxygen gas, which is present in the atmosphere at aconcentration of at least about 300 ppm (i.e., 300 moles of O₂ per1,000,000 moles of total gas). More preferably, the oxygen concentrationis from about 300 to about 2000 ppm, and most preferably from about 300to about 500 ppm. The remainder of the oxidizing atmosphere preferablyconsists essentially of a gas which will not react with the siliconsurface or the oxidant. More preferably, the remainder of the gasconsists essentially of a noble gas or N₂, more preferably a noble gas,and most preferably Ar. The oxidizing atmosphere preferably is exposedto at least the epitaxial surface during the heating. More preferably,the oxidizing atmosphere is exposed to essentially the entire surface ofthe wafer. Most preferably, the oxidizing atmosphere is exposed to theentire surface of the wafer, minus the portion of the wafer which is incontact with the structure supporting the wafer in the furnace.

Following the heat treatment of the wafer in the oxidizing atmosphere,the wafer is rapidly cooled. This cooling step may conveniently becarried out in the same oxidizing atmosphere in which the heat-treatmentis conducted. Alternatively, it preferably is carried out in anatmosphere that will not react with the wafer surface. Preferably, thewafer is cooled at a rate of at least about 10° C./sec. More preferably,the wafer is cooled at a rate of at least about 15° C./sec., even morepreferably at least about 20° C./sec., and most preferably at leastabout 50° C./sec. This rapid cooling rate preferably is used as thetemperature of the wafer decreases through the range of temperatures atwhich crystal lattice vacancies diffuse through the single crystalsilicon. Once the wafer is cooled to a temperature outside the range oftemperatures at which crystal lattice vacancies are relatively mobile,the cooling rate does not significantly influence the precipitatingcharacteristics of the wafer, and, thus, is not narrowly critical.Generally, crystal lattice vacancies are relatively mobile attemperatures greater than about 1000° C.

In a particularly preferred embodiment, the average cooling rate of thewafer is at least about 10° C./sec. (more preferably at least about 15°C./sec., still more preferably at least about 20° C./sec., and mostpreferably at least about 50° C./sec.) as its temperature falls from thesoak temperature to a temperature which is about 150° C. less than thesoak temperature. In another particularly preferred embodiment, theaverage cooling rate of the wafer is at least about 10° C./sec. (morepreferably at least about 15° C./sec., still more preferably at leastabout 20° C./sec., and most preferably at least about 50° C./sec.) asits temperature falls from the soak temperature to a temperature whichis about 250° C. less than the soak temperature.

The heating and rapid cool-down may be carried out, for example, in anyof a number of commercially available rapid thermal annealing (“RTA”)furnaces in which wafers are heated by banks of high power lamps. RTAfurnaces are capable of rapidly heating a silicon wafer. For example,many are capable of heating a wafer from room temperature to 1200° C. ina few seconds. Examples of suitable commercially available furnacesinclude the model 610 furnace from AG Associates (Mountain View, Calif.)and the CENTURA® RTP from Applied Materials (Santa Clara, Calif.).

Alternatively, the heating and rapid cool-down may be carried out in anepitaxial deposition reactor, provided that the desired cooling rate canbe achieved in the reactor. Applicants have determined that the heatingand cooling steps can be carried out in an EPI CENTURA® reactor.Referring to FIG. 3 and FIG. 7, such a reactor includes a susceptor 101for supporting a wafer. The susceptor 101 is fixedly mounted on arms 103of a susceptor support shaft 105 slidingly mounted within a bore 106 ofa wafer lift shaft 107. The wafer lift shaft is mounted for verticalmovement within a cylindrical opening in a lower dome (not shown) of thereactor. A pneumatic mechanism (not shown) is operable to move thesusceptor support shaft 105 and the wafer lift shaft 107 vertically,either together or independently as desired. The mechanism is furtheroperable to rotate the susceptor support shaft 105 within the bore 106so that the susceptor 101 and wafer may be rotated. The susceptorincludes rigid pins 109 slidingly mounted in openings in the susceptorto engage stops 111 of the wafer lift shaft at their lower ends. Theupper ends of the pins 109 are capable of supporting the wafer.Conventionally, the pins 109 have only been used to support the waferduring transfer to and from the reactor.

To position the wafer for heat-treatment in the EPI CENTURA® reactor,the wafer is delivered to the reactor, such as by blade 113, which issized to fit between the rigid pins 109 (see FIG. 7). The susceptorsupport shaft 105 and wafer lift shaft 107 are moved upward from theexchange position shown in FIG. 3 to the home position shown in FIG. 4.The upward motion of the susceptor support shaft 105 causes the pins 109(which are engaged with the wafer lift shaft 107) to engage the backsurface of the wafer and lift the wafer off of the blade 113. The bladeis thereafter removed from the reactor. Referring to FIG. 5, thesusceptor support shaft 105 is then moved further upward while the waferlift shaft 107 remains stationary. This causes the pins 109 to slidedownwardly relative to the susceptor 101 until the upper surface of thesusceptor 101 is brought into contact with the wafer. Thereafter, thesusceptor 101 supports the wafer. Meanwhile, the support shaft 105continues to move upward until the susceptor 101 is coplanar with ring115. At this point, the susceptor is in the process position. A bank ofhigh power lamps (not shown) is then activated to heat the wafer whileit is supported by the susceptor 101 in the process position.Preferably, the susceptor 101 and wafer are rotated while being heatedso that the wafer is heated more uniformly.

It has been found that the typical average cooling rate (i.e., about 10to 15° C./sec.) of a wafer in the EPI CENTURA® reactor tends to be farless than the typical average cooling rate (i.e., about 70 to 100°C./sec) that may be achieved in an RTA furnace at temperatures wherecrystal lattice vacancies are relatively mobile. This is, in part, dueto the fact that the susceptor 101 (see FIG. 5), which is in contactwith the wafer, remains hot for some time after heating is completed. Toincrease the cooling rate, therefore, the wafer preferably is moved to aposition as far as possible from the susceptor 101. This may beaccomplished by lowering the susceptor support shaft 105 to the exchangeposition shown in FIG. 6 immediately after heating is complete. In theexchange position, the wafer is supported only by the pins 109, so thatsubstantially all the back surface and all the front surface of thewafer are not in contact with any other solid hot surfaces (besides thepins 109). Further, the wafer is positioned as far as possible from thehot susceptor 101. By lifting the wafer off of the susceptor 101, therate of cooling of the wafer may be approximately doubled (i.e., theaverage rate of cooling increases from a range of from about 10 to 15°C./sec to a range of from about 25 to about 30° C./sec).

The non-uniform vacancy profile prepared in accordance with thisinvention is a template for oxygen precipitation when the wafer issubsequently heated. Specifically, when the wafer 1 (see FIG. 2) isheated, oxygen will cluster rapidly to form precipitates 52 in theregion 17 of the wafer 1 containing higher concentrations of vacancies,but will tend not to cluster in the regions 15 and 15′ near the wafersurfaces 3 and 5 which contain lower concentrations of vacancies.Typically, the oxygen nucleates at temperatures of from about 500 toabout 800° C., and grows precipitates at temperatures of from about 700to about 1000° C. Thus, for example, the non-uniform distribution ofoxygen precipitates 52 in a wafer may be formed during a heat treatmentcycle of an electronic device manufacturing process, given that suchheat treatment cycles often are conducted at temperatures near 800° C.

As discussed previously, it is particularly advantageous to use thisinvention to treat a void-rich wafer starting material, which has arelatively large number of COPs on its surface and voids within itsbulk. FIG. 8 shows an example of a crystal lattice vacancy agglomerate51 profile and oxygen precipitate 52 profile for an epitaxial waferprepared from a void-rich wafer starting material using the process ofthe instant invention, followed by heat-treatment. An epitaxial layer 50is on the outer surfaces 3, 4, and 6 (no epitaxial layer is on the backsurface 5 in this particular embodiment) of the wafer 1. Because theepitaxial layer has filled in essentially all the COPs, the wafer hassmooth, essentially COP-free surface 2 and 8. Preferably, this epitaxialsurface has an average light scattering event concentration of nogreater than about 0.06/cm², as measured by a laser-based autoinspection tool configured to detect light scattering eventscorresponding to polystyrene spheres having diameters of no less thanabout 0.12 μm. The profile of the oxygen precipitates 52 is similar tothe oxygen precipitate profile in FIG. 2, and is sufficient forintrinsic gettering. The profile of the vacancy agglomerates 51completely within the bulk (i.e., the profile of the voids within thebulk) of the wafer 1 essentially remains the same throughout the processof this invention, and does not tend to affect the surfaces 2 and 8 ofthe wafer 1 due to the existence of the epitaxial layer 50, which actsas a barrier between the surfaces 2 and 8 and the agglomerates 51. Thus,this invention is commercially useful, in part, because it enables theformation of a silicon wafer having intrinsic gettering ability and anessentially COP-free surface from a void-rich wafer starting material,which may be prepared with relatively low cost.

If a void-rich wafer starting material is used, the wafer produced inaccordance with this invention typically may be characterized in that asurface on the wafer may be produced which has an average lightscattering event concentration of at least about 0.5/cm² (as measured bya laser-based auto inspection tool configured to detect light scatteringevents corresponding to polystyrene spheres having diameters of no lessthan about 0.12 μm) if the epitaxial layer and a layer of siliconextending at least 0.2 μm beneath the epitaxial layer (i.e., a layerwhich has a thickness of at least 0.2 μm as measured from the epitaxiallayer toward the central plane of the wafer) is removed from the wafer.In a particularly preferred embodiment, this light scattering eventconcentration is from about 0.5 to about 10/cm², more preferably fromabout 0.5 to about 3.5/cm², and most preferably from about 0.6 to about1.6/cm². The epitaxial layer and the additional layer of silicon may beremoved from the front surface by various polishing and cleaningtechniques which are generally known and accepted by those skilled inthe art. Preferably, the polishing and cleaning technique is capable,under at least some circumstances, of polishing and cleaning a surfaceof a single crystal silicon wafer having a resistivity of less thanabout 0.02 Ω-cm to form a surface having an average light scatteringevent concentration of no greater than about 0.2/cm² (again, as measuredby a laser-based auto inspection tool configured to detect lightscattering events corresponding to polystyrene spheres having diametersof no less than about 0.12 μm).

The above description of the preferred embodiment is intended only toacquaint others skilled in the art with the invention, its principles,and its practical application, so that others skilled in the art mayadapt and apply the invention in its numerous forms, as may be bestsuited to the requirements of a particular use. The present invention,therefore, is not limited to the above embodiments, and may be variouslymodified.

1. A single crystal silicon wafer comprising: (a) two major generallyparallel surfaces, one of which is a front surface of the wafer and theother of which is a back surface of the wafer; (b) a central planebetween and parallel to the front and back surfaces; (c) a front surfacelayer which comprises the region of the wafer extending a distance, D₁,of at least about 10 μm from the front surface toward the central plane;and (d) a bulk layer which comprises the region of the wafer extendingfrom the central plane to the front surface layer, the wafer beingcharacterized in that: the wafer has a non-uniform distribution ofcrystal lattice vacancies wherein (a) the bulk layer has a crystallattice vacancy concentration which is greater than in the front surfacelayer, (b) the crystal lattice vacancies have a concentration profilehaving a peak density of crystal lattice vacancies at or near thecentral plane, and (c) the concentration of crystal lattice vacanciesgenerally decreases from the position of peak density toward the frontsurface of the wafer; and the front surface of the wafer has anepitaxial layer deposited thereon, the epitaxial layer having athickness of at least about 0.1 μm.
 2. The single crystal silicon waferof claim 1 wherein D₁ is from about 50 to about 100 μm.
 3. The singlecrystal silicon wafer of claim 1 wherein the resistivity of the wafer is1.0 to about 20 Ω-cm. 4-10. (canceled)
 11. A single crystal siliconwafer comprising: (a) two major generally parallel surfaces, one ofwhich is a front surface of the wafer and the other of which is a backsurface of the wafer; (b) a central plane between and parallel to thefront and back surfaces; (c) a front surface layer comprising the regionof the wafer extending a distance of no greater than about 100 μm fromthe front surface toward the central plane; and (d) a bulk layercomprising the region of the wafer extending from the central plane tothe front surface layer, wherein the bulk layer has a substantiallyuniform oxygen concentration and a concentration of crystal latticevacancies such that upon subjecting the wafer to an oxygen precipitationheat treatment consisting essentially of annealing the wafer at 800° C.for about 4 hours and then at 1000° C. for 16 hours, the wafer willcontain oxygen precipitates having a concentration profile in which thepeak density of the precipitates in the bulk layer is at or near thecentral plane with the concentration of the precipitates in the bulklayer generally decreasing toward the front surface layer; and the frontsurface of the wafer has an epitaxial layer deposited thereon, theepitaxial layer having a thickness of at least about 0.1 μm. 12-13.(canceled)
 14. A process for the preparation of a silicon wafercomprising a surface having an epitaxial layer deposited thereon, theprocess comprising: heating a surface of a wafer starting material in anessentially oxidant-free atmosphere to remove a silicon oxide layer fromthe surface; within about 30 seconds after removing the silicon oxidelayer from the surface, exposing the surface to an atmosphere comprisingsilicon to deposit a silicon epitaxial layer onto the surface to form anepitaxial wafer; heating the epitaxial wafer to a soak temperature of atleast about 1175° C. while exposing the epitaxial layer to an oxidizingatmosphere comprising an oxidant; and cooling the heated epitaxial waferat a rate of at least about 10° C./sec.
 15. The process of claim 14wherein the oxidant in the oxidizing atmosphere is O₂.
 16. The processof claim 14 wherein the cooling rate is at least about 15° C./sec. 17.The process of claim 14 wherein, while the wafer starting material isexposed to the atmosphere comprising silicon, the wafer startingmaterial is maintained at an epitaxial deposition temperature at whichthe atmosphere comprising silicon will not deposit polycrystallinesilicon onto the heated surface when the atmosphere is contacted withthe heated surface.
 18. The process of claim 14 wherein the waferstarting material is maintained at an epitaxial deposition temperatureof at least about 900° C. while the wafer starting material is exposedto the atmosphere comprising silicon.
 19. The process of claim 14wherein the wafer starting material is maintained at an epitaxialdeposition temperature of from about 1050 to about 1150° C. while thewafer starting material is exposed to the atmosphere comprising silicon.20. The process of claim 14 wherein the silicon oxide layer is removedfrom the surface of the wafer starting material by heating the surfaceto a temperature of at least about 1150° C.
 21. The process of claim 14wherein within about 10 seconds after removing the silicon oxide layerfrom the surface, the surface is exposed to the atmosphere comprisingsilicon to deposit the silicon epitaxial layer onto the surface to formthe epitaxial wafer.
 22. A process for the preparation of a siliconwafer comprising a surface having an epitaxial layer deposited thereon,the process comprising: heating a surface of a wafer starting materialto a temperature of at least about 1100° C. in an essentiallyoxidant-free atmosphere to remove a silicon oxide layer from thesurface, within about 30 seconds after the surface reaches 1100° C.,exposing the surface to an atmosphere comprising silicon to deposit asilicon epitaxial layer onto the surface to form an epitaxial wafer,heating the epitaxial wafer to a soak temperature of at least about1175° C. while exposing the epitaxial layer to an oxidizing atmospherecomprising an oxidant, and cooling the heated epitaxial wafer at a rateof at least about 10° C./sec.
 23. The process of claim 22 wherein theatmosphere comprising silicon comprises SiCl₄, SiHCl₃, SiH₂Cl₂, SiH₃Cl,or SiH₄.
 24. The process of claim 22 wherein the atmosphere comprisingsilicon comprises SiHCl₃.
 25. The process of claim 22 wherein the waferstarting material is maintained at an epitaxial deposition temperatureof at least about 900° C. while the wafer starting material is exposedto the atmosphere comprising silicon.
 26. The process of claim 22wherein the cooling rate is at least about 15° C./sec.
 27. The processof claim 22 wherein the average cooling rate of the wafer is at leastabout 15° C./sec as it cools from the soak temperature to about 150° C.below the soak temperature.
 28. The process of claim 22 wherein thecooling rate is at least about 20° C./sec.
 29. The process of claim 22wherein the average cooling rate of the wafer is at least about 20°C./sec as it cools from the soak temperature to about 150° C. below thesoak temperature.
 30. The process of claim 22 wherein the cooling rateis at least about 50° C./sec.
 31. The process of claim 22 wherein theaverage cooling rate of the wafer is at least about 50° C./sec as itcools from the soak temperature to about 150° C. below the soaktemperature.
 32. The process of claim 22 wherein the resistivity of thewafer starting material is 1.0 to about 20 Ω-cm.
 33. The process ofclaim 22 wherein the epitaxial wafer is maintained at the soaktemperature for from about 10 to about 15 seconds before it is cooled.34. The process of claim 22 wherein the process comprises: heating thesurface of the wafer starting material to a temperature of at leastabout 1100° C. in the essentially oxidant-free atmosphere to remove thesilicon oxide layer from the surface, and within about 20 seconds afterthe surface reaches 1100° C., exposing the surface to the atmospherecomprising silicon to deposit the silicon epitaxial layer onto thesurface to form the epitaxial wafer.
 35. The process of claim 22 whereinthe process comprises: heating the surface of the wafer startingmaterial to a temperature of at least about 1100° C. in the essentiallyoxidant-free atmosphere to remove the silicon oxide layer from thesurface, and within about 10 seconds after the surface reaches 1100° C.,exposing the surface to the atmosphere comprising silicon to deposit thesilicon epitaxial layer onto the surface to form the epitaxial wafer.36. The process of claim 22 wherein the heating and cooling of theepitaxial wafer are conducted in a reactor constructed for depositing asilicon epitaxial layer onto a surface of a wafer, and the epitaxialwafer is supported on a susceptor during the heating step and is removedfrom contact with the susceptor during the cooling step.
 37. A processfor the preparation of a silicon wafer comprising a surface having anepitaxial layer deposited thereon, the process comprising: heating asurface of a wafer starting material to a temperature of at least about1150° C. in an essentially oxidant-free atmosphere to remove a siliconoxide layer from the surface, within about 30 seconds after the surfacereaches 1150° C., exposing the surface to an atmosphere comprisingsilicon to deposit a silicon epitaxial layer onto the surface to form anepitaxial wafer, heating the epitaxial wafer to a soak temperature of atleast about 1175° C. while exposing the epitaxial layer to an oxidizingatmosphere comprising an oxidant, and cooling the heated epitaxial waferat a rate of at least about 10° C./sec.
 38. The process of claim 37wherein the process comprises: heating the surface of the wafer startingmaterial to a temperature of at least about 1150° C. in the essentiallyoxidant-free atmosphere to remove the silicon oxide layer from thesurface, and within about 20 seconds after the surface reaches 1150° C.,exposing the surface to the atmosphere comprising silicon to deposit thesilicon epitaxial layer onto the surface to form the epitaxial wafer.39. The process of claim 37 wherein the process comprises: heating thesurface of the wafer starting material to a temperature of at leastabout 1150° C. in the essentially oxidant-free atmosphere to remove thesilicon oxide layer from the surface, and within about 10 seconds afterthe surface reaches 1150° C., exposing the surface to the atmospherecomprising silicon to deposit the silicon epitaxial layer onto thesurface to form the epitaxial wafer.
 40. The process of claim 37 whereinthe average cooling rate of the wafer is at least about 15° C./sec as itcools from the soak temperature to about 150° C. below the soaktemperature.
 41. The process of claim 37 wherein the average coolingrate of the wafer is at least about 20° C./sec as it cools from the soaktemperature to about 150° C. below the soak temperature.
 42. The processof claim 37 wherein the average cooling rate of the wafer is at leastabout 50° C./sec as it cools from the soak temperature to about 150° C.below the soak temperature.
 43. A process for the preparation of asilicon wafer comprising a surface having an epitaxial layer depositedthereon, the process comprising: depositing an epitaxial layer onto asurface of a wafer to form an epitaxial wafer, heating the epitaxialwafer to a soak temperature of at least about 1175° C. while exposingthe epitaxial layer to an oxidizing atmosphere comprising an oxidant,and cooling the heated epitaxial wafer at a rate of at least about 10°C./sec., wherein the epitaxial layer is not contacted with apost-epitaxial-deposition cleaning solution before the epitaxial waferis heated to the soak temperature.
 44. The process of claim 43 whereinthe oxidant is O₂.
 45. A process for the preparation of a silicon wafercomprising a surface having an epitaxial layer deposited thereon,wherein the epitaxial layer has a thickness of at least about 0.1 μm andless than 2.0 μm, and the process comprises: heating a wafer comprisinga surface with an epitaxial layer deposited thereon to a soaktemperature of at least about 1175° C. while exposing the epitaxiallayer to an oxidizing atmosphere comprising an oxidant, and cooling theheated wafer at a rate of at least about 10° C./sec.
 46. The process ofclaim 45 wherein the oxidant is O₂.
 47. The process of claim 45 whereinthe epitaxial layer has a thickness of from about 0.25 to about 1.0 μm.48. The process of claim 45 wherein the epitaxial layer has a thicknessof from about 0.65 to about 1.0 μm.
 49. A process for the preparation ofa silicon wafer comprising a surface having an epitaxial layer depositedthereon, the process comprising: depositing an epitaxial layer onto asurface of a wafer starting material to form an epitaxial wafer, heatingthe epitaxial wafer to a soak temperature of at least about 1175° C.while exposing the epitaxial layer to an oxidizing atmosphere comprisingan oxidant, and cooling the heated epitaxial wafer at a rate of at leastabout 10° C./sec., wherein the surface of the wafer starting material,before deposition of the epitaxial layer thereon, has an average lightscattering event concentration of at least about 0.5/cm² as measured bya laser-based auto inspection tool configured to detect light scatteringevents corresponding to polystyrene spheres having diameters of no lessthan about 0.12 μm.
 50. The process of claim 49 wherein the averagelight scattering event concentration is from about 0.5 to about 10/cm².51. The process of claim 49 wherein the average light scattering eventconcentration is from about 0.5 to about 3.5/cm².
 52. The process ofclaim 49 wherein the average light scattering event concentration isfrom about 0.6 to about 1.6/cm².
 53. A process for the preparation of asilicon wafer comprising a surface having an epitaxial layer depositedthereon, the process comprising: heating a surface of a wafer startingmaterial to a temperature of at least about 1150° C. in an atmosphereconsisting essentially of H₂ to remove a silicon oxide layer from thesurface, within about 10 seconds after the surface reaches 1150° C.,exposing the surface to an atmosphere comprising SiHCl₃ to deposit asilicon epitaxial layer onto the surface to form an epitaxial wafer,heating the epitaxial wafer to a soak temperature of at least about1175° C. while exposing the epitaxial layer to an oxidizing atmospherecomprising O₂, and cooling the heated epitaxial wafer from the soaktemperature to 250° C. below the soak temperature at an average rate ofat least about 20° C./sec, wherein the epitaxial layer has a thicknessof from about 0.65 to 1.0 μm, and the concentration of the O₂ in theoxidizing atmosphere is from about 300 to about 500 ppm.
 54. A processfor heating and rapidly cooling a single crystal silicon wafer in areactor constructed for depositing a silicon epitaxial layer onto asurface of a wafer, the process comprising the steps of: heating thewafer to a soak temperature of at least about 1175° C., and cooling theheated wafer at a rate of at least about 10° C./sec., wherein the waferis supported on a susceptor during the heating step and is removed fromcontact with the susceptor during the cooling step.
 55. The process ofclaim 54 wherein the cooling rate is at least about 15° C./sec.
 56. Theprocess of claim 54 wherein the cooling rate is at least about 20°C./sec.
 57. The process of claim 54 wherein the cooling rate is fromabout 25 to about 30° C./sec.
 58. The process of claim 54 wherein thewafer is supported on pins during the cooling step.